Substitution reactions that employ primary-carbamoyl-protected arylmethanethiols are described. The enantiodetermining step was found to occur in the post-deprotonation step as a dynamic thermodynamic resolution with a chiral bis(oxazoline) ligand. The configurationally labile lithium complexes were trapped with various electrophiles to yield different substitution products in good to excellent yields and enantiomeric excesses. The absolute configurations of the substitution products were determined, and the stereochemical pathway of the substitution reaction was elucidated for different classes of electrophiles. The temperature-dependent epimerization process was monitored by 1H and 6Li NMR spectroscopy.
Lange, H., Bergander, K., Frohlich, R., Kehr, S., Nakamura, S., Shibata, N., et al. (2008). Highly Enantioselective Reactions of Configurationally Labilem Epimeric Diamine Complexes of Lithiated S-Benzyl Thiocarbamates. CHEMISTRY - AN ASIAN JOURNAL, 3(1), 88-101 [10.1002/asia.200700262].
Highly Enantioselective Reactions of Configurationally Labilem Epimeric Diamine Complexes of Lithiated S-Benzyl Thiocarbamates
Lange, H;
2008
Abstract
Substitution reactions that employ primary-carbamoyl-protected arylmethanethiols are described. The enantiodetermining step was found to occur in the post-deprotonation step as a dynamic thermodynamic resolution with a chiral bis(oxazoline) ligand. The configurationally labile lithium complexes were trapped with various electrophiles to yield different substitution products in good to excellent yields and enantiomeric excesses. The absolute configurations of the substitution products were determined, and the stereochemical pathway of the substitution reaction was elucidated for different classes of electrophiles. The temperature-dependent epimerization process was monitored by 1H and 6Li NMR spectroscopy.File | Dimensione | Formato | |
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Lange et al. Benzylthiocarbamates_Chem. Asian J. 2008, 3, 88-101.pdf
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